Abstract

A combined in-situ investigation using X-ray diffraction and differential scanning calorimetry during annealing was carried out to investigate the formation of intermetallic compounds in the stacked elemental layers and to reveal its influences on the crystallization of kesterite Cu2ZnSnSe4. The Mo/Cu/Zn, Mo/Cu/Sn/Zn, Mo/Cu/Zn/Se and Mo/Cu/Sn/Zn/Se stacked films were prepared with a composition resembling a typical kesterite Cu-poor and Zn-rich metallic composition. In-situ experiments during annealing of pure metallic stacked films reveal a dynamic intermetallic compounds formation of Cu5Zn8 -> CuZn -> Cu2Zn -> Cu3Zn and Cu6Sn5 -> Cu41Sn11. The Cu-Zn and Cu5Zn8 layer formed at the interface of metals/Se may prevent the stacked metallic layers from selenization below 320 degrees C. On the other side, the dynamic formation of Cu-Zn phases in the stacked films is found to be an origin of a ZnSe gradual formation starting from 320 degrees C. Phase analysis suggests that the ternary Cu2SnSe3 phase forms almost immediately after the formation of Cu2Se and SnSe. The formation of Cu2SnSe3 is indicated by the consumption of SnSe by the Cu2Se which occurs at 530-540 degrees C. Crystallization of kesterite takes place above 540 degrees C. On a phenomenological basis of present results, consequences for the thin film kesterite fabrication for solar cell application are discussed. (C) 2013 Elsevier B.V. All rights reserved.